Primary aromatic amine formaldehyde resins and compositions and methods of making the same



Patented June 19, 19

PRIMARY AROMATIC AIWINE FORMALDE- HYDE RESINS AND COMPOSITIONS AND METHODS OF MAKING THE SAME Loring Coes', Jr., Brookfield, Masa, assignor to Norton Company, Worcester, Mass, acorporation of Massachusetts No Drawing. Application July 23, 1942,

Serial No. 452,089

This invention relates to resins and more particularly to the polymerized condensation-product of a primary aromatic amine with formaldehyde.

One object of the inventionis to provide a reagent which hardens or'conve'rts' to an infusible condition a primary aromatic amine formaldehyde resin and particularly an aniline formaldehyde resin.

Another object is to provide an agent which not only hardens such resins but will also serve as a wettant for granular material bonded by the resin and as a plasticizer for the green mixture of grains and resin prior to the heat hardening stage.

Another object of the invention is to provide a hardening agent for such resins which during the heat conversion stage will not react to form water and cause distortion of the resin body.

Another object of the invention is to provide a method of making a final resin product, or an intermediate product capable of producing the same, whereby a primary aromatic amine formaldehyde resin may-be materially hardened.

Another object'is to provide a method of this type wherein 'a resin or a mixture of the resin with granular material to be bonded thereby may be cold-molded and the molded object thereafter heat cured while not confined under pressure.

Another object is to provide a method of making molded objects, with or without granular material, with the aid of an agent serving as a wettant and a plasticizer for a primary aromatic amine formaldehyde resin prior to heat hardening and which" ultimately acts'as a hardening and cross-linking agent for the resin without producing water during the hardening stage or causing distortion of the formed body; Other objects will be in part obvious or in part pointed out hereinafter,

The invention accordingly consists in the compositions and products, and in the several steps and relation and orderof each of said steps to one or more of theothers thereof, all as will be illustratively described herein, and the scope of the application of which will be indicated in the following claims.

My invention consists in the use of the chloracetates of the glyceroldichlorhydrins as alkylating'and cross-linking agents or hardening agents for the primary aromatic amine formaldehye resins; and these agents may be used with or without other halogenated alk-ylating compounds, with or without fillers, and with or without the use of supplemental wettant plasticizers, such as furi'ural. I have found that these chloracetates can be used as wettants for granular material, such en the resin as abrasive grains, bonded by this type of resin and that they will serve as a plasticizer for the green mixture of granular material and resin prior to the heat hardening stage; but the esters serve primarily as cross-linking agents that hard- V when the mixture is subjected to heat.

I provide a quantity of primary aromatic amine, such as aniline, ortho, meta or para toluidine,

or diamino diphenyl methane; and a quantity of formaldehyde. I may optionally provide, to supplement the above-mentioned chloracetate a quantity of one or more organic compounds containing a halogen selected from the group consisting of chlorine, bromine and iodine and capable of splitting oil hydrogen halide at elevated temperatures and/or of alkylating an aromatic amine polymer, providing cross links connecting amine groups of the chains. The aromatic amine which I now prefer to use is aniline. Aniline Y or one of the other aromatic amines mentioned,

or mixtures of two or more of such amines, is

' reacted with formaldehyde HCHO in the presence stable and will not alkylate the polymer. Howof a strong acid to produce along chain polymer which, when an excess of formaldehyde above the stoichiometric proportions is used, for example, 20% excess, has adjacent chains connected with methylene CH2- groups to form a tough, heat resistant, semi-thermoplastic resin. I may add some of the formaldehyde after the initial condensation, in the form of paraformaldehyde, or by the addition of hexa-methylene-tetramine.

As examples of the supplemental halogenated organic compound, I may use any of polyvinyl chloride, polyvinylidene dichloride, rubber hydrochloride, chlorinated rubber, chlorinated polyiso butylene; any chlorine, bromine or iodine substituted parafilne hydrocarbon, such as hexa chlor ethane, tetrai chlor pentane, 1, 2, diiodo ethane, beta butylene bromide, partly chlorinated eicosane, or any aliphatic halohydrin of not more than six carbon atoms, such as any of the amylene chlorhydrins; propylene chlorhydrin; any of the butylene chlorhydrins; ethylene chlorhydrin, ethylene bromhydrin, or glycerol alpha gamma diclorhydrin. Naturally enough, most of the examples are chlorinated compounds because these are cheaper and more readily available than the brominated or iodated compounds, but the latter two give eflecitve results, The fiuorinated compounds are rejected because they are too been used as this plasticizer-wettant.

ever, so far as the broad features of this invention are concerned, and apart from the esters hereinafter described, the halogenated organic compound may be omitted altogether.

Since one use of the resins or the invention relates to grinding wheels and other solid abrasive compositions and articles, I provide a quantity of abrasive grain. Any abrasive grain may be used, for example, any of the varieties of alumina, such as emery, corundum, dense "regular fused alumina, porous white fused alumina; silicon carbide and other hard carbides; quartz;

glass; garnet; or diamonds. Two or more of these abrasives may be mixed, if desired.

Manufacturers usually prefer to use the dry granular mix method, with the cold press and the oven to make organic bonded grinding wheels because this combination of steps and features is the cheapest to carry out and furthermore, generally gives uniform results. In the dry granular mix method the abrasive grains are placed in a mixing pan and are then wet with a suitable liquid; thenpowdered fusible resin is added, mixing is'done to coat each granule withsome ofthe powder and to leave a minimum of loose powder, then amold is charged withthe dry granular mix thus produced, the top plate. is inserted, the mold is closed by means of an hydraulic press, the mold is then stripped," the green" wheel is taken to an oven and (at the same time as hundreds or thousands of others of varying sizes, shapes and compositions) it is cured to make the final composition and, after truing" 0r "shaving," the final article. This method, in contradistinction to the use of the r hot press with or without the autoclave and vice versa, has the advantage that ordinary ovens, in which thousands of green wheels can be stacked, are used; the hydraulic press is tied up by a given wheel for thirty seconds instead of thirty minutes, and the press need have no heated platens. This wetting of the abrasive grains by a liquid is called plasticizing." It is Preferred that the wettant be a solvent for the resin.

In the commercial manufacture of anilineformaldehyde resin bonded grinding wheels and other solid abrasive products, only furfural has (Other aromatic-amine-aldehyde polymers have not been used commercially for the manufacture of grlnding wheels and other solid abrasive products so far as I am aware). The furfural cross links the polymer and, therefore, converts it to the infusible condition. A stoichiomet'ric quantity of aniline and formaldehyde condensed in the presence of a strong acid is believed to produce a resin whichis structurally represented thus:

11 n n 11 O Q CW- t y g t i Such a resin cross-linked with furfural is believed to be represented thus:

l e-n In accordance with my invention, the chloracetates of glycerol dichlorhydrins may be used as alkylating and cross-linking agents for the primary Laromatic amine formaldehyde resins. A preferred and illustrative method of carrying out my invention may be as follows: I first prepare the chloracetate. For example, I may start with glycerol a'y dichlorhydrin and glycerol afl dichlorhydrin, which are respectively, or may be written thus: a

I C Ha-Cl and C Hz-Cl These are estersandthe mixture alkylates and cross-links, I believe, the aniline-formaldehyde,

thus:

- nae-c1 til,"-

I It will be noted that chlorine now appears .in the more and is a higher heat than generated in amino group. When a grinding wheel according to the invention is used to grind, the'heat generated by grinding (which may reach 500 C. or

most sanding operations with sandpaper or the like) reelases hydrogen chloride at the grinding line which appears to have a pronounced effect upon the grinding operation, preventing or at least "loading" and assisting in the cutting action by making the metal chips more brittle.

Grinding wheels when made according to my invention achieve a number or practical advantages and the abrasive article may be madeup without having to tie up expensive hot-press equipment, and several methods, illustrations of which are later set forth, may be used where it is not desired to resort to hot-pressing. Thus the mix of resin (in powder form), abrasive. I

grains, and chloracetate hardening agent, with or without other ingredients, fillers, or the like, may be shaped in any desired way cold, or at room temperature, and after such shaping may be put in an oven for heat treatment to cure the resin and effect the bonding together of the abrasive articles. Grinding wheels made according to my invention have or may be given, in general, cutting characteristics similar to those of hard-rubber bonded wheels, and thus maybe used to perform grinding operations where such hard rubber-bonded wheels are preferred or more suitable.

, throughout.

made free from localized mechanical weaknesses However, my invention consists also in the discovery that the above-mentioned esters are good solvents or hardening agents for the primary aromatic amine formaldehyde resins and that thereby I am enabled to produce a resin, with or without fillers or the like, that is strong and tough and that may be used for the making of various" the above-mentioned polymer not only hydrogen chloride, but also do so in a manner to free hydrogen chloride at the grinding line, under the heat effect produced during grinding. Moreover, the esters are good wettants for the abrasive grains and this is of great advantage in that thereby it is made certain that each grain becomes well coated by and with the particles of the powdered resin and thus there is good assurance of achieving, during the curing, good and uniform bonding of the abrasive grains, the

abrasive article having thereby substantial uniformity of strength and other characteristics The abrasive wheel, can thus be and its wear can be uniform.

There are hereinafter. set forth several examples illustrating preferred methods of making grinding wheels according to certain aspects of my invention, but it may here be pointed out that those examples will also sufl'lce to illustrate or indicate how I may achieve the production, by

of a resin or resinous grams of c'hloracetic acid and the mixture is' pressure, say, at 20 millimeters, for about 3 hours.

The product is light yellow brown in color and has a slight pleasant odor. It is a good solvent for aniline formaldehyde resin.

Example I 4 525 grams of #46 grit "l ilundum abrasive grain is wet with 20' cc. of the above-mentioned product which may be termed glycerol dichlorhy- -drin chloracetate and thereto is added, with stirring, 165 grams of a mixture, by volume, of 65% of aniline formaldehyde resin, 30% of cryolite, and

5% of soluble anhydrite, resulting in a dry granular mix." The latter is spread in a 6" mold, where a grinding wheel is'to be made, and pressed to the. desired pore volume, in this in stance, 15 percent. The green wheel 'is' then stripped from the mold and cured in an oven. Preferably, I utilize an initial curing temperature of 95 C., gradually raising the temperature, over a period of 4 hours, to about 175 C., and

i n 3 then keep the temperature at 175 C. for about Zhouts, and then cool the wheel oil.

' 'Emample II 525 grams of #80 grit Alundum abrasive grain is wet with 25 cc. of the above-mentioned mixture of esters and thereto is then added, with stirring, 165 grams of a mixture, by volume, of

65% of aniline formaldehyde resin, 30% of cryolite, and 5% of soluble anhydrite, resulting in a dry granular mix.

The latter is then worked on rolls until the desired thickness is achieved, in this instance, From the resultant sheet, a 12" disk is then cut and the resultant green wheel is then heat-treated, preferably in the manner described above in Example I.

It will be understood that either of the esters or mixtures thereof may be used, following substantially the proportions of materials illustrated in the foregoing two specific examples, and whether either ester alone or the two in admixture are employed, it will be seen that, in the cross-linking with the above-mentioned polymer, the same relationships appear, including the appearance of the hydrogen chloride at the amino groups. r

Wheels so made, running at a surface speed of 9500 feet per minute, when testedin'grinding cold rolled steel showed an areal wheel wear of 0.043 square inch per cut when running wet and 0.075 square inch per cut when running dry.

35 A wheel made according to Example I was tested as a portable snagging ,wheel with good results; its resiliency was of such an order as to. greatly facilitate manual control of the positioning or movement of the wheel and the pressure of its application and"; gave the wheel a free cutting and smooth action. I y 1 According to certain prior practices, difficulties are encountered during heat treatment or curing, due to the fact that swelling occurs; such swelling usually results from the formation of water and is aggravated by the conversion of water or possibly also of other constituents into vapors, under the action of the heat treatment. But according to my invention such disadvantages and defects are successfully overcome and I flnd that,

in practicing my invention, no such swelling 0c curs; this is due to the fact that no water or r 1 other liquid or vapors'thereof, as would cause swelling, during the formed.

It will be understood that either of the abovementioned esters maybe usedalone or they may both be used in admixture; in any such case the cross-linking is as above set forth in con- 0 nection with the mixture of both esters. In the illustrations above set forth, I have used mix tures simply because of the convenience in using commercially available already-mixed glycerol dichlorhydrlns of the two types; when reacted 35 with chloracetic acid as above described, :a mixture ofthe two chloracetates results. The illustrations above set forth are, therefore, notto be interpreted by way of limitation.

I make no claim herein to abrasive articles or 7 /to the method of. making the same, since these are claimed in my Patent No. 2,319,791 of May It will thus be seen that there has been provided by this invention, an article, acomposition and a method in which the various obiects differential mixing rolls until formed into substantially a sheet 0 and the sheet is then passed through calender heat treatment or curing, are

hereinabove set forth together with many thoroughly practical advantages are successfully achieved. As various possible embodiments might be made of the various features of the above invention and as the art, herein described might be varied in various parts, all without departing from the scope of the invention, it is to be understood that all matter hereinbefore set forthis to be interpreted as illustrative and not in a limiting sense.

I claim: e 1. An intermediate product that is moldable ment comprising a mixture of a primary aromatic amine formaldehyde resin and a hardenlng agent therefor comprising essentially a chloracetate of glycerol dichlorhydrln.

2. A resinous product comprising a primary aromatic amine formaldehyde resin alkylated by and cross-linked with a hardening agent comprising essentially a chloracetate ofglycerol di chlorhydrin.

3. A resinous product comprising a primary aromatic amine formaldehyde resin'cross -linked with an alkylating agent comprising essentially the esters of chloracetic acid with glycerol u'y dichlorhydrin and glycerol 415 dichlorhydrln.

- and capable of being hardened under heat treat- 15A resinous product comprising aniline formaldehyde resin alkylated by and cross-linked with a hardening agent comprising essentially a chloracetate of glycerol dichlorhydrln.

5. The method of making a resinous product which comprises mixing a primary aromatic amine formaldehyde resin with a chloracetateof glycerol dichlorhydrin and heat treating the 7 mixture to react the resin and said ester.

6. The method of making an intermediate product that is moldable and capable of being hardened under heat treatment which comprlsesmixing a primary aromatic amine formaldehyde resin with a cross-linking and alkylating agent selected from the group consisting of the chloracetic acid esters of glycerol a7 dichlorhyd'rin and glycerol up dichlorhydrin and a mixture thereof.

7. The method of making a resinous product which comprises mixing a powdered primary aromatie amine formaldehyde resin with a crosslinking and alkylating agent comprising essenv tially a chloracetic acid ester of glyceroldichlorhydrin, cold-molding the mixture and subsequently heat treating the molded article to cause said ester to react with the resin and thereby hardening the mass. I

LORING GOES, JR. 

